Stereodivergent Assembling Tsuji–Trost Reaction via Photoinduced Pd and Pd/Ir Relay Catalysis

Tsuji-Trost reaction typically relies on the use of alkenes containing an α-leaving group as the substrates. In comparison, an in situ assembling model from feedstock chemicals represents a distinctive and practically valuable route, yet remains undeveloped. Here we report an unprecedented excited Pd-catalyzed in situ assembling Tsuji-Trost reaction by using readily available alkenes, esters, and nucleophiles as substrates. With the development of a HAT/Heck/allylation cascade protocol, various (E)-allyl compounds are prepared in good yields and stereoselectivities. Meanwhile, a novel photoinduced Pd/Ir relay catalysis is designed to enable stereoselective preparation of challenging (Z)-allyl compounds. Stereodivergent synthesis of all four stereoisomers [(E,R), (E,S), (Z,R), and (Z,S)] is also realized via this excited-state Pd chemistry, different from typical ground-state catalytic models. A broad range of N-, C-, O-, and S-derived nucleophiles and different alkenes and esters show high compatibility with the transformation. The protocol is further applied to the concise synthesis of seven bioactive molecules from bulk materials, highlighting the reliability, generality, and practical value of the design. Mechanistic studies support the present design.